Ethylenic polymer and its use

ABSTRACT

New ethylene polymers having low levels of long chain branching are disclosed. Films and film layers made form these polymers have good hot tack strength over a wide range of temperatures, making them good materials for packaging applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. ProvisionalApplication No. 61/222,367, filed on Jul. 1, 2009 and a second filedU.S. Provisional Application No. 61/222,367 filed on Aug. 7, 2009, andfully incorporated herein.

BACKGROUND OF THE INVENTION

Metallocene-catalyzed polymers have been commercial for several years,and are used in many end-use applications, such as packaging, personalhygiene, automotive, flooring, adhesives, fibers, nonwovens, films,sheets, and fabrics. The metallocene-catalyzed polymers have certainadvantages, such as narrow molecular weight distributions. Some of themetallocene-catalyzed polymers are homogeneous polymers that have longchain branching which enhances their processability. However,metallocene-catalyzed polymers are still subject to degradation underultraviolet light and have cross-linking characteristics that make theiruse in certain applications more challenging. Further, thosemetallocene-catalyzed polymers which have relatively high levels of longchain branching typically exhibit poor hot tack strength and/or a narrowsealing window, which renders them less useful in certain filmapplications.

Known metallocene-catalyzed polymers include both (a) thehomogeneous-branched, substantially linear ethylene polymers (“SLEP”)which are prepared using constrained geometry catalysts (“CGCCatalyst”), such as disclosed in U.S. Pat. No. 5,272,236 and U.S. Pat.No. 5,278,272, and WO93/08221, as well as the homogeneous linearethylene polymers (“LEP”) which are prepared using other metallocene(called “bis-CP catalysts”). Various grades of SLEPs, having a varietyof densities and melt flow rates, are commercially available from TheDow Chemical Company as ENGAGE™ polyolefin elastomers or AFFINITY™plastomers. Various grades of LEPs are commercially available fromExxonMobil Chemical Company as EXAC™ or EXCEED™ polymers.

A characteristic of metallocene-catalyzed polymers is that they have asignificant level (typically in excess of 300 wppm) of residualunsaturation, with that unsaturation being in various combinations andamounts of one or more of the following unsaturated groups:

Vinyl, vinylidene, vinylene, vinyl-3, and tri-substituted vinyls.

Such residual unsaturations, and particularly the vinyl-3 groups, arebelieved to contribute to long-term polymer degradation, as well as todifficulties in controlling either or both of desired cross-linking insome applications or undesired cross-linking (such as the formation ofgels) in other end-use applications (such as films).

Further, for film applications, it is desirable to have a broad thermalbonding window (temperature range) as well as relatively low hot tackinitiation temperature.

BRIEF SUMMARY OF THE INVENTION

This invention is related to new essentially linear polyethylene resinshaving a very low level of long chain branching. Such resins have 110/12(measured at 190° C.) from about 5.8 to about 6.5, preferably from about5.9 to about 6.5; a zero shear viscosity (ZSV) ratio of from about 1.3to about 2.3, preferably from about 1.4 to about 2.2, most preferablyfrom about 1.5 to about 2.1 and Mw/Mn of from about 2.0 to about 2.4,preferably from about 2.1 to about 2.3. Such resins can have melt index(190° C., 2.16 kg load) from about 0.5 to about 15 grams/10 minutes,preferably from about 0.7 to about 12. Such resins can also have a DSCmelting point defined by the relationship,

Tm (° C.)≦(−7914.1*(density)2)+(15301*density)−7262.4, where density isin g/cc. The density of the polymers can be from about 0.857 g/cc to0.905 g/cc, preferably from about 0.865 g/cc to 0.905 g/cc, mostpreferably from about 0.885 g/cc to 0.905 g/cc.

In a first aspect of the invention, there is provided an ethylenicpolymer comprising.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows hot tack data for two ethylenic polymers of the inventionmade into film layers and for a comparative example.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“Composition,” as used, includes a mixture of materials which comprisethe composition, as well as reaction products and decomposition productsformed from the materials of the composition.

“Blend” or “polymer blend,” as used, mean an intimate physical mixture(that is, without reaction) of two or more polymers. A blend may or maynot be miscible (not phase separated at molecular level). A blend may ormay not be phase separated. A blend may or may not contain one or moredomain configurations, as determined from transmission electronspectroscopy, light scattering, x-ray scattering, and other methodsknown in the art. The blend may be effected by physically mixing the twoor more polymers on the macro level (for example, melt blending resinsor compounding) or the micro level (for example, simultaneous formingwithin the same reactor).

“Linear,” as used, refers to polymers where the polymer backbone of thepolymer lacks measurable or demonstrable long chain branches, forexample, the polymer is substituted with an average of less than 0.01long branch per 1000 carbons.

“Polymer” refers to a polymeric composition prepared by polymerizingmonomers, whether of the same or a different type. The generic term“polymer” thus embraces the term “homopolymer,” usually employed torefer to polymers prepared from only one type of monomer, and the term“interpolymer” as defined. The terms “ethylene/α-olefin polymer” isindicative of interpolymers as described.

“Interpolymer,” as used, refers to polymers prepared by thepolymerization of at least two different types of monomers. The genericterm interpolymer includes copolymers (usually employed to refer topolymers prepared from two different monomers) and polymers preparedfrom more than two different types of monomers.

“Ethylenic polymer” refers to a polymer that contains more than 50 molepercent polymerized ethylene monomer (based on the total amount ofpolymerizable monomers) and, optionally, may contain one or morecomonomers.

The term “ethylene/α-olefin interpolymer” refers to an interpolymer thatcontains more than 50 mole percent polymerized ethylene monomer (basedon the total amount of polymerizable monomers) and at least oneα-olefin.

Test Methods and Measurements

Density: The density of a polymer (g/cm³) is measured according toASTM-D 792-03, Method B, in isopropanol. Specimens are measured within 1hour of molding after conditioning in the isopropanol bath at 23° C. for8 min to achieve thermal equilibrium prior to measurement. The specimensare compression molded according to ASTM D-4703-00 Annex A with a 5 mininitial heating period at about 190° C. and a 15° C./min cooling rateper Procedure C. The specimen is cooled to 45° C. in the press withcontinued cooling until “cool to the touch.”

Melt Indices and Melt Index Ratio: The melt index (I₂) of a polymer ismeasured in accordance with ASTM D 1238, Condition 190° C./2.16 kg, andis reported in grams eluted per 10 minutes, and the melt index (I₁₀) ismeasured in accordance with ASTM D 1238, Condition 190° C./10 kg, and isreported in grams eluted per 10 minutes. The melt index ratio (I₁₀/I₂)is a ratio of these two melt indices.

Differential Scanning calorimetry: Differential Scanning calorimetry(DSC) can be used to measure the melting and crystallization behavior ofa polymer over a wide range of temperature. For example, the TAInstruments Q1000 DSC, equipped with an RCS (refrigerated coolingsystem) and an autosampler is used to perform this analysis. Duringtesting, a nitrogen purge gas flow of 50 ml/min is used. Each sample ismelt pressed into a thin film at about 175° C.; the melted sample isthen air-cooled to room temperature (˜25° C.). A 3-10 mg, 6 mm diameterspecimen is extracted from the cooled polymer, weighed, placed in alight aluminum pan (ca 50 mg), and crimped shut. Analysis is thenperformed to determine its thermal properties. The thermal behavior ofthe sample is determined by ramping the sample temperature up and downto create a heat flow versus temperature profile. First, the sample israpidly heated to 180° C. and held isothermal for 3 minutes in order toremove its thermal history. Next, the sample is cooled to −40° C. at a10° C./minute cooling rate and held isothermal at −40° C. for 3 minutes.The sample is then heated to 150° C. (this is the “second heat” ramp) ata 10° C./minute heating rate. The cooling and second heating curves arerecorded. The cool curve is analyzed by setting baseline endpoints fromthe beginning of crystallization to −20° C. The heat curve is analyzedby setting baseline endpoints from −20° C. to the end of melt. Thevalues determined are peak melting temperature (T_(m)), peakcrystallization temperature (T_(c)), heat of fusion (H_(f)) (in Joulesper gram), and the calculated % crystallinity for polyethylene samplesusing:

%Crystallinity=((H _(f))/(292 J/g))×100.

The heat of fusion (H_(f)) and the peak melting temperature are reportedfrom the second heat curve. Peak crystallization temperature isdetermined from the cooling curve.

Molecular Weight Measurements by Triple Detector Gel PermeationChromatography (3D-GPC)

The 3D-GPC system consists of a Polymer Laboratories (Shropshire, UK)Model 210 equipped with an on-board differential refractometer (RI).Additional detectors can include Precision Detectors (Amherst, Mass.)2-angle laser light scattering detector Model 2040, and a Viscotek(Houston, Tex.) 150R 4-capillary solution viscometer. The 15-degreeangle of the light scattering detector is used for calculation purposes.Data collection can be performed using Viscotek TriSEC software, Version3, and a 4-channel Viscotek Data Manager DM400. The system is alsoequipped with an on-line solvent degassing device from PolymerLaboratories (Shropshire, UK). Suitable high temperature GPC columnssuch as 30 cm Polymer Labs columns of 10-micron mixed-pore-size packing(Mixed-B). The sample carousel compartment is operated at 145° C. andthe column compartment is operated at 145° C. The samples are preparedat a concentration of 0.025 g of polymer in 20 mL of solvent. Thechromatographic solvent contains 100 ppm and the sample preparationsolvent contains 200 ppm of butylated hydroxytoluene (BHT). Bothsolvents are sparged with nitrogen. The polyethylene samples are gentlyshaken every 30 minutes while maintaining 160° C. for 2.5-3.0 hours. Theinjection volume is 200 microliters. The flow rate through the GPC isset at 1 mL/minute.

The GPC column set is calibrated before running the polymer by runningtwenty narrow molecular weight distribution polystyrene standards. Themolecular weight (MW) of the standards ranges from 580 to 8,400,000g/mol, and the standards are contained in 6 “cocktail” mixtures. Eachstandard mixture has at least a decade of separation between individualmolecular weights. The standards are purchased from Polymer Laboratories(Shropshire, UK). The polystyrene standards are prepared at 0.005 g in20 mL of solvent for molecular weights equal to or greater than1,000,000 g/mol and 0.001 g in 20 mL of solvent for molecular weightsless than 1,000,000 g/mol. The polystyrene standards were dissolved atroom temperature with gentle agitation for four hours. The narrowstandards mixtures are run first and in order of decreasing highestmolecular weight component to minimize degradation. A logarithmicmolecular weight calibration is generated using a fifth-order polynomialfit as a function of elution volume. The absolute molecular weights wereobtained in a manner consistent with that published by Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P.,Classical Light Scattering from Polymer Solutions, Page 113-136,Elsevier, Oxford, N.Y. (1987)). The response factor of the laserdetector and the viscometer were determined using the certificated valuefor the weight average molecular weight (52,000 g/mol, dn/dc=0.104 mL/g)and intrinsic viscosity (1.01 dL/g) of NIST 1475. The mass constant ofthe differential refractive index detector was determined using the areaunder the curve, concentration, and injection volume of the broadpolyethylene homopolymer. The chromatographic concentrations wereassumed low enough to eliminate addressing 2nd Virial coefficienteffects (concentration effects on molecular weight).

The Systematic Approach for the determination of each detector offsetwas implemented in a manner consistent with that published by Balke,Mourey, et. Al (Mourey and Balke, Chromatography Polym. Chpt 12, (1992))(Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt13, (1992)), using data obtained from the three detectors whileanalyzing a broad linear polystyrene homopolymer and the narrowpolystyrene standards,

g′(HMW)/g′(LMW) Determination

The g′ was defined as the ratio of measured intrinsic viscosity [η] ofpolymer divided by the intrinsic viscosity [η]_(linear) of a linearpolymer having the same molecular weight. A value of g′ is often usedfor indication of branching in a polymer. For the purpose of thisinvention, g′ is defined as the same comonomer level for the inventivepolymer and the linear polymer.

A value of g′(HMW)/g′(LMW) is a measure of the branching leveldifference between the highest and lowest molecular weight ranges. Forlinear polymers, the g′(HMW)/g′(LMW) value equals 1.0 and for branchedpolymer this value is less than 1.0.

The g′(HMW)/g′(LMW) value was calculated using 3D-GPC. A value of g′₁,the g′ value at i^(th) fraction in the polymer molecular weightdistribution was calculated. The polymer molecular weight distributioncurve was normalized and weight fraction at i^(th) molecular weight wascalculated.

The g′(HMW) was calculated by the weighted mean value of g′ calculatedfor the 30% of polymer with highest molecular weight,

${g^{\prime}({HMW})} = {\frac{\sum\limits_{i}^{\;}\left( {g_{i}^{\prime} \times w_{i}} \right)}{\sum\limits_{i}^{\;}w_{i}} = \frac{\sum\limits_{i}^{\;}\left( {g_{i}^{\prime} \times w_{i}} \right)}{0.30}}$

here w_(i) is the i^(th) fraction of polymers within the 30% of polymerswith highest molecular weight, and g′ is the [η]/[η]_(linear) value inthe same i^(th) fraction.

The g′(LMW) was calculated in the same way, where w_(i) is the i^(th)fraction of polymers within the 30% of polymers with lowest molecularweight.

${g^{\prime}({LMW})} = {\frac{\sum\limits_{j}^{\;}\left( {g_{j}^{\prime} \times w_{j}} \right)}{\sum\limits_{j}^{\;}w_{j}} = \frac{\sum\limits_{j}^{\;}\left( {g_{j}^{\prime} \times w_{j}} \right)}{0.3}}$

Creep Zero Shear Viscosity Method

Specimens for creep measurements were prepared on a programmableTetrahedron bench top press. The program held the melt at 177° C. for 5minutes at a pressure of 10⁷ Pa. The chase was then removed to thebenchtop to cool down to room temperature. Round test specimens werethen die-cut from the plaque using a punch press and a handheld die witha diameter of 25 mm. The specimen is about 1.8 mm thick.

Zero-shear viscosities are obtained via creep tests that are conductedon an AR-G2 stress controlled rheometer (TA Instruments; New Castle,Del.) using 25-mm-diameter parallel plates at 190° C. The rheometer ovenis set to test temperature for at least 30 minutes prior to zeroingfixtures. At the testing temperature a compression molded sample disk isinserted between the plates and allowed to come to equilibrium for 5minutes. The upper plate is then lowered down to 50 μm above the desiredtesting gap (1.5 mm). Any superfluous material is trimmed off and theupper plate is lowered to the desired gap. Measurements are done undernitrogen purging at a flow rate of 5 L/min. Default creep time is setfor 2 hours.

A constant low shear stress of 20 Pa is applied for all of the samplesto ensure that the steady state shear rate is low enough to be in theNewtonian region. The resulting steady state shear rates are in theorder of 10⁻³ s⁻¹ for the samples in this study. Steady state isdetermined by taking a linear regression for all the data in the last10% time window of the plot of log(J(t)) vs. log(t), where J(t) is creepcompliance and t is creep time. If the slope of the linear regression isgreater than 0.97, steady state is considered to be reached, then thecreep test is stopped. In all cases in this study the slope meets thecriterion within 30 minutes. The steady state shear rate is determinedfrom the slope of the linear regression of all of the data points in thelast 10% time window of the plot of ε vs. t, where ε is strain. Thezero-shear viscosity is determined from the ratio of the applied stressto the steady state shear rate.

In order to determine if the sample is degraded during the creep test, asmall amplitude oscillatory shear test is conducted before and after thecreep test on the same specimen from 0.1 to 100 rad/s at 10% strain. Thecomplex viscosity values of the two tests are compared. If thedifference of the viscosity values at 0.1 rad/s is greater than 5%, thesample is considered to have degraded during the creep test, and theresult is discarded.

ZSVR Definition:

Zero-shear viscosity ratio (ZSVR) is defined as the ratio of thezero-shear viscosity (ZSV) of the inventive polymer to the ZSV of alinear polyethylene material at the equivalent weight average molecularweight (M_(w-gpc)) as shown in the equation below.

${ZSVR} = \frac{\eta_{0}}{\eta_{0\; L}}$

The η₀ value (in Pa·s) is obtained from creep test at 190° C. via themethod described above. It is known that ZSV of linear polyethyleneη_(0L) has a power law dependence on its M_(w) when the M_(w) is abovethe critical molecular weight M_(c). An example of such a relationshipis described in Karjala et al. (Annual Technical Conference—Society ofPlastics Engineers (2008), 66^(th), 887-891) as shown in the equationbelow and it is used in the present invention to calculate the ZSVRvalues.

η_(0L)=2.29×10⁻¹⁵ M _(w-gpc) ^(3.65)

The M_(w-gpc) value in the equation (in g/mol) is determined by usingthe GPC method as defined in the next section.

M_(w-gpc) Determination

To obtain M_(w-gpc) values, the chromatographic system consisted ofeither a Polymer Laboratories Model PL-210 or a Polymer LaboratoriesModel PL-220. The column and carousel compartments were operated at 140°C. Three Polymer Laboratories 10-μm Mixed-B columns were used with asolvent of 1,2,4-trichlorobenzene. The samples were prepared at aconcentration of 0.1 g of polymer in 50 mL of solvent. The solvent usedto prepare the samples contained 200 ppm of the antioxidant butylatedhydroxytoluene (BHT). Samples were prepared by agitating lightly for 4hours at 160° C. The injection volume used was 100 microliters and theflow rate was 1.0 mL/min. Calibration of the GPC column set wasperformed with twenty one narrow molecular weight distributionpolystyrene standards purchased from Polymer Laboratories. Thepolystyrene standard peak molecular weights were converted topolyethylene molecular weights using

M _(polyethylene) =A(M _(polystyrene))^(B)  (3)

where M is the molecular weight, A has a value of 0.4316 and B is equalto 1.0. A third order polynomial was determined to build the logarithmicmolecular weight calibration as a function of elution volume.Polyethylene equivalent molecular weight calculations were performedusing Viscotek TriSEC software Version 3.0. The precision of theweight-average molecular weight ΔM_(w,2s) was excellent at <2.6%.

Gel Rating of the Polymers.

Method/Description of GI200 Test

Extruder: Model OCS ME 20 available from OCS Optical Control SystemsGmbH Wullener Feld 36, 58454 Witten, Germany or equivalent.

Parameter Standard Screw L/D 25/1 Coating Chrome Compression ratio  3/1Feed Zone 10D Transition Zone  3D Metering Zone 12D Mixing Zone —Cast Film Die: ribbon die, 150×0.5 mm, available from OCS OpticalControl Systems GmbH, or equivalent.Air Knife: OCS air knife to pin the film on the chill roll, availablefrom OCS Optical Control Systems GmbH, or equivalent.Cast Film Chill Rolls and Winding Unit: OCS Model CR-8, available fromOCS Optical Control Systems GmbH, or equivalent.

Profile Number 070 071 072 MELT INDEX dg/min 0.1-1.2 1.2-3.2 3.2-32Density g/cm³ ALL ALL ALL Throat ° C. 25 ± 3 25 ± 3 25 ± 3 Zone 1 ° C.180 ± 5  160 ± 5  140 ± 5  Zone 2 ° C. 240 ± 5  190 ± 5  170 ± 5  Zone 3° C. 260 ± 5  200 ± 5  175 ± 5  Zone 4 ° C. 260 ± 5  210 ± 5  175 ± 5 Adapter ° C. 260 ± 5  225 ± 5  180 ± 5  Die ° C. 260 ± 5  225 ± 5  180 ±5  Screw Type Standard Standard Standard Screw Speed RPM 70 ± 2 70 ± 270 ± 2 Air Knife Flow Nm³/h  6 ± 2  6 ± 2  6 ± 2 Die to Chill Roll mm  6± 1  6 ± 1  6 ± 1 Die to Air Knife mm  6 ± 1  6 ± 1  6 ± 1 Chill Speedm/min.  3 ± 1  3 ± 1  3 ± 1 Chill Temp. ° C. 20 ± 2 20 ± 2 20 ± 2Tension Speed m/min.  6 ± 2  6 ± 2  6 ± 2 Winder Torque N  8 ± 1  8 ± 1 8 ± 1 Lab Temperature ° C. 23 ± 2 23 ± 2 23 ± 2 Lab Humidity % <70 <70<70 Width mm 108 ± 18 108 ± 18 108 ± 18 Thickness μm 76 ± 5 76 ± 5 76 ±5 Gel Counter: OCS FS-3 line gel counter consisting of a lighting unit,a CCD detector and an image processor with the Gel counter softwareversion 3.65e 1991-1999, available from OCS Optical Control SystemsGmbH, or equivalent. The OCS FS-5 gel counter is equivalent.Instantaneous GI200 Note: GI stands for “gel index”. GI200 includes allgels ≧200 μm in diameter.

The instantaneous GI200 is the sum of the area of all the size classesin one analysis cycle:

$X_{j} = {\sum\limits_{k = 1}^{4}A_{T,j,k}}$

where:

X_(j)=instantaneous GI200 (mm²/24.6 cm³) for analysis cycle j 4=totalnumber of size clauses

GI200

GI200 is defined as the trailing average of the last twentyinstantaneous G1200 values:

$< X>={\sum\limits_{j = 1}^{20}{X_{j}/20}}$

where:

<X>=GI200(mm²/24.6 cm³)

One analysis cycle inspects 24.6 cm³ of film. The corresponding area is0.324 m² for a film thickness of 76 μm and 0.647 m² for a film thicknessof 38 μm.

Gel Content Measurement: When the ethylene interpolymer, either alone orcontained in a composition is at least partially crosslinked, the degreeof crosslinking may be measured by dissolving the composition in asolvent for specified duration, and calculating the percent gel orunextractable component. The percent gel normally increases withincreasing crosslinking levels.

Long chain branching per 1000 carbons: The presence of long chainbranching can be determined in ethylene homopolymers by using ¹³Cnuclear magnetic resonance (NMR) spectroscopy and is quantified usingthe method described by Randall (Rev. Macromol. Chem. Phys., C29, V.2&3, 285-297). There are other known techniques useful for determiningthe presence of long chain branches in ethylene polymers, includingethylene/1-octene interpolymers. Two such exemplary methods are gelpermeation chromatography coupled with a low angle laser lightscattering detector (GPC-LALLS) and gel permeation chromatographycoupled with a differential viscometer detector (GPC-DV). The use ofthese techniques for long chain branch detection and the underlyingtheories have been well documented in the literature. See, for example,Zimm, G. H. and Stockmayer, W. H., J. Chem. Phys., 17, 1301 (1949), andRudin, A., Modern Methods of Polymer Characterization, John Wiley &Sons, New York (1991) 103-112.

Hot Tack Testing of Films: Hot Tack testing can be determined inaccordance to Strength (Hot Tack) of Thermoplastic Polymers and BlendsComprising the Sealing Surfaces of Flexible Webs as referenced in ASTMF-1921_(—)04.

Ethylenic polymers of this Invention: The ethylenic polymers of thisinvention are relatively high molecular weight, relatively low densitypolymers that have a unique combination of (A) a relatively low totalamount of unsaturation, and (B) a relatively high ratio of vinyl groupsto total unsaturated groups in the polymer chain, as compared to knownmetallocene-catalyzed ethylenic polymers. This combination is believedto result in lower gels for end-use applications (such as films) wherelow gels are important, better long-term polymer stability and, forend-use applications requiring cross-linking, better control of thatcross-linking, in each case while maintaining a good balance of otherperformance properties.

The novel polymers of this invention are interpolymers of ethylene withat least 0.1 mole percent of one or more comonomers, preferably at leastone α-olefin comonomer. The α-olefin comonomer(s) may have, for example,from 3 to 20 carbon atoms. Preferably, the α-olefin comonomer may have 3to 8 carbon atoms. Exemplary α-olefin comonomers include, but are notlimited to, propylene, 1-butene, 3-methyl-1-butene, 1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene,4,4-dimethyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-nonene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Preparation of an Ethylenic Polymer of this Invention

For producing the ethylenic polymers of this invention, a solution-phasepolymerization process may be used. Typically, such a process occurs ina well-stirred reactor such as a loop reactor or a sphere reactor attemperature from about 150 to about 300° C., preferably from about 160to about 180° C., and at pressures from about 30 to about 1000 psi,preferably from about 30 to about 750 psi. The residence time in such aprocess is typically from about 2 to about 20 minutes, preferably fromabout 10 to about 20 minutes. Ethylene, solvent, catalyst, and one ormore comonomers are fed continuously to the reactor. Exemplary solventsinclude, but are not limited to, isoparaffins. For example, suchsolvents are commercially available under the name ISOPAR E fromExxonMobil Chemical Co., Houston, Tex. The resultant mixture ofethylene-based polymer and solvent is then removed from the reactor andthe polymer is isolated. Solvent is typically recovered via a solventrecovery unit, that is, heat exchangers and vapor liquid separator drum,and is recycled back into the polymerization system.

Suitable catalysts for use in preparing the novel polymers of thisinvention include any compound or combination of compounds that isadapted for preparing such polymers in the particular type ofpolymerization process, such as solution-polymerization,slurry-polymerization or gas-phase-polymerization processes.

In one embodiment, an ethylenic polymer of this invention is prepared ina solution-polymerization process using a polymerization catalyst thatis a metal complex of a polyvalent aryloxyether corresponding to theformula:

where M³ is Ti, Hf or Zr, preferably Zr;

Ar⁴⁺ independently each occurrence is a substituted C₉₋₂₀ aryl group,wherein the substituents, independently each occurrence, are selectedfrom the group consisting of alkyl; cycloalkyl; and aryl groups; andhalo-, trihydrocarbylsilyl- and halohydrocarbyl-substituted derivativesthereof, with the proviso that at least one substituent lacksco-planarity with the aryl group to which it is attached;

T⁴ independently each occurrence is a C₂₋₂₀ alkylene, cycloalkylene orcycloalkenylene group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy ordi(hydrocarbyl)amino group of up to 50 atoms not counting hydrogen;

R³ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen, or two R³ groups on the samearylene ring together or an R³ and an R²¹ group on the same or differentarylene ring together form a divalent ligand group attached to thearylene group in two positions or join two different arylene ringstogether; and

R^(D), independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a hydrocarbylene, hydrocarbadiyl, diene, orpoly(hydrocarbyl)silylene group.

Such polyvalent aryloxyether metal complexes and their synthesis aredescribed in WO 2007/136496 or WO 2007/136497, using the synthesisprocedures disclosed in US-A-2004/0010103. Among the preferredpolyvalent aryloxyether metal complexes are those disclosed as example 1in WO 2007/136496 and as example A10 in WO 2007/136497. Suitablecocatalysts and polymerization conditions for use of the preferredpolyvalent aryloxyether metal complexes are also disclosed in WO2007/136496 or WO 2007/136497.

The metal complex polymerization catalyst may be activated to form anactive catalyst composition by combination with one or more cocatalysts,preferably a cation forming cocatalyst, a strong Lewis acid, or acombination thereof. Suitable cocatalysts for use include polymeric oroligomeric aluminoxanes, especially methyl aluminoxane, as well asinert, compatible, noncoordinating, ion forming compounds. So-calledmodified methyl aluminoxane (MMAO) or triethyl aluminum (TEA) is alsosuitable for use as a cocatalyst. One technique for preparing suchmodified aluminoxane is disclosed in U.S. Pat. No. 5,041,584 (Crapo etal.). Aluminoxanes can also be made as disclosed in U.S. Pat. Nos.5,542,199 (Lai et al.); 4,544,762 (Kaminsky et al.); 5,015,749 (Schmidtet al.); and 5,041,585 (Deavenport et al.).

Polymeric Blends or Compounds of this invention: Various natural orsynthetic polymers, and/or other components, may be blended orcompounded with the novel polymers of this invention to form thepolymeric compositions of this invention. Suitable polymers for blendingwith the embodiment ethylenic polymer include thermoplastic andnon-thermoplastic polymers including natural and synthetic polymers.Suitable synthetic polymers include both ethylene-based polymers, suchas high pressure, free-radical low density polyethylene (LDPE), andethylene-based polymers prepared with Ziegler-Natta catalysts, includinghigh density polyethylene (HDPE) and heterogeneous linear low densitypolyethylene (LLDPE), ultra low density polyethylene (ULDPE), and verylow density polyethylene (VLDPE), as well as multiple-reactor ethylenicpolymers (“in reactor” blends of Ziegler-Natta PE and metallocene PE,such as products disclosed in U.S. Pat. Nos. 6,545,088 (Kolthammer etal.); 6,538,070 (Cardwell et al.); 6,566,446 (Parikh et al.); 5,844,045(Kolthammer et al.); 5,869,575 (Kolthammer et al.); and 6,448,341(Kolthammer et al.)). Commercial examples of linear ethylene-basedpolymers include ATTANE™ Ultra Low Density Linear PolyethyleneCopolymer, DOWLEX™ Polyethylene Resins, and FLEXOMER™ Very Low DensityPolyethylene, all available from The Dow Chemical Company. Othersuitable synthetic polymers include polypropylene, (both impactmodifying polypropylene, isotactic polypropylene, atactic polypropylene,and random ethylene/propylene copolymers), ethylene/diene interpolymers,ethylene-vinyl acetate (EVA), ethylene/vinyl alcohol copolymers,polystyrene, impact modified polystyrene, ABS, styrene/butadiene blockcopolymers and hydrogenated derivatives thereof (SBS and SEBS), andthermoplastic polyurethanes. Homogeneous olefin-based polymers such asethylene-based or propylene-based plastomers or elastomers can also beuseful as components in blends or compounds made with the ethylenicpolymers of this invention. Commercial examples of homogeneousmetallocene-catalyzed, ethylene-based plastomers or elastomers includeAFFINITY™ polyolefin plastomers and ENGAGE™ polyolefin elastomers, bothavailable from The Dow Chemical Company, and commercial examples ofhomogeneous propylene-based plastomers and elastomers include VERSIFY™performance polymers, available from The Dow Chemical Company, andVISTAMAX™ polymers available from ExxonMobil Chemical Company.

The polymeric compositions of this invention include compositionscomprising, or made from, the ethylenic polymer of this invention incombination (such as blends or compounds, including reaction products)with one or more other components, which other components may include,but are not limited to, natural or synthetic materials, polymers,additives, reinforcing agents, ignition resistant additives, fillers,waxes, tackifiers, antioxidants, stabilizers, colorants, extenders,crosslinkers, blowing agents, and/or plasticizers. Such polymericcompositions may include thermoplastic polyolefins (TPO), thermoplasticelastomers (TPE), thermoplastic vulcanizates (TPV) and/orstyrenic/ethylenic polymer blends. TPEs and TPVs may be prepared byblending or compounding one or more ethylenic polymers of this invention(including functionalized derivatives thereof) with an optionalelastomer (including conventional block copolymers, especially an SBS orSEBS block copolymer, or EPDM, or a natural rubber) and optionally acrosslinking or vulcanizing agent. A TPO polymeric composition of thisinvention would be prepared by blending or compounding one or more ofthe ethylenic polymers of this invention with one or more polyolefins(such as polypropylene). A TPE polymeric composition of this inventionwould be prepared by blending or compounding one or more of theethylenic polymers of this invention with one or more elastomers (suchas a styrenic block copolymer or an olefin block copolymer, such asdisclosed in U.S. Pat. No. 7,355,089 (Chang et al.)). A TPV polymericcomposition of this invention would be prepared by blending orcompounding one or more of the ethylenic polymers of this invention withone or more other polymers and a vulcanizing agent.

The foregoing polymeric compositions may be used in forming a moldedobject, and optionally crosslinking the resulting molded article. Asimilar procedure using different components has been previouslydisclosed in U.S. Pat. No. 6,797,779 (Ajbani, et al.).

Processing Aids: In certain aspects of the invention, processing aids,such as plasticizers, can also be included in the polymeric composition.These aids include, but are not limited to, the phthalates (such asdioctyl phthalate and diisobutyl phthalate), natural oils (such aslanolin, and paraffin, naphthenic and aromatic oils obtained frompetroleum refining), and liquid resins from rosin or petroleumfeedstocks. Exemplary classes of oils useful as processing aids includewhite mineral oil such as KAYDOL® oil (Chemtura Corp.; Middlebury,Conn.) and SHELLFLEX® 371 naphthenic oil (Shell Lubricants; Houston,Tex.). Another suitable oil is TUFFLO® oil (Lyondell Lubricants;Houston, Tex.).

Stabilizers and other additives: In certain aspects of the invention,the ethylenic polymers are treated with one or more stabilizers, forexample, antioxidants, such as IRGANOX® 1010 and IRGAFOS® 168 (CibaSpecialty Chemicals; Glattbrugg, Switzerland). In general, polymers aretreated with one or more stabilizers before an extrusion or other meltprocesses. For example, the compounded polymeric composition maycomprise from 200 to 600 wppm of one or more phenolic antioxidants,and/or from 800 to 1200 wppm of a phosphite-based antioxidant, and/orfrom 300 to 1250 wppm of calcium stearate. In other aspects of theinvention, other polymeric additives are blended or compounded into thepolymeric compositions, such as ultraviolet light absorbers, antistaticagents, pigments, dyes, nucleating agents, fillers, slip agents, fireretardants, plasticizers, processing aids, lubricants, stabilizers,smoke inhibitors, viscosity control agents, and/or anti-blocking agents.The polymeric composition may, for example, comprise less than 10percent by the combined weight of one or more of such additives, basedon the weight of the ethylenic polymer.

Other additives: Various other additives and adjuvants may be blended orcompounded with the ethylenic polymers of this invention to formpolymeric compositions, including fillers (such as organic or inorganicparticles, including nano-size particles, such as clays, talc, titaniumdioxide, zeolites, powdered metals), organic or inorganic fibers(including carbon fibers, silicon nitride fibers, steel wire or mesh,and nylon or polyester cording), tackifiers, waxes, and oil extenders(including paraffinic or naphthelenic oils), sometimes in combinationwith other natural and/or synthetic polymers.

Cross-linking Agents: For those end-use applications in which it isdesired to fully or partially cross-link the ethylenic polymer of thisinvention, any of a variety of cross-linking agents may be used. Somesuitable cross-linking agents are disclosed in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 14, pages 725-812 (2001); Encyclopedia ofChemical Technology, Vol. 17, 2nd edition, Interscience Publishers(1968); and Daniel Seem, “Organic Peroxides,” Vol. 1,Wiley-Interscience, (1970). Non-limiting examples of suitablecross-linking agents include peroxides, phenols, azides, aldehyde-aminereaction products, substituted ureas, substituted guanidines;substituted xanthates; substituted dithiocarbamates; sulfur-containingcompounds, such as thiazoles, sulfenamides, thiuramidisulfides,paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; imidazoles;silanes and combinations thereof. Non-limiting examples of suitableorganic peroxide cross-linking agents include alkyl peroxides, arylperoxides, peroxyesters, peroxycarbonates, diacylperoxides,peroxyketals, cyclic peroxides and combinations thereof. In someembodiments, the organic peroxide is dicumyl peroxide,t-butylisopropylidene peroxybenzene, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl-cumyl peroxide, di-t-butyl peroxide,2,5-dimethyl-2,5-di-(t-butyl peroxy)hexyne or a combination thereof. Inone embodiment, the organic peroxide is dicumyl peroxide. Additionalteachings regarding organic peroxide cross-linking agents are disclosedin C. P. Park, “Polyolefin Foam”, Chapter 9 of Handbook of Polymer Foamsand Technology, edited by D. Klempner and K. C. Frisch, HanserPublishers, pp. 198-204, Munich (1991). Non-limiting examples ofsuitable azide cross-linking agents include azidoformates, such astetramethylenebis(azidoformate); aromatic polyazides, such as4,4′-diphenylmethane diazide; and sulfonazides, such asp,p′-oxybis(benzene sulfonyl azide). The disclosure of azidecross-linking agents can be found in U.S. Pat. Nos. 3,284,421 and3,297,674. In some embodiments, the cross-linking agents are silanes.Any silane that can effectively graft to and/or cross-link theethylene/α-olefin interpolymer or the polymer blend disclosed herein canbe used. Non-limiting examples of suitable silane cross-linking agentsinclude unsaturated silanes that comprise an ethylenically unsaturatedhydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl,cyclohexenyl or gamma-(meth)acryloxy allyl group, and a hydrolyzablegroup such as a hydrocarbyloxy, hydrocarbonyloxy, and hydrocarbylaminogroup. Non-limiting examples of suitable hydrolyzable groups includemethoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, alkyl and arylaminogroups. In other embodiments, the silanes are the unsaturated alkoxysilanes which can be grafted onto the interpolymer. Some of thesesilanes and their preparation methods are more fully described in U.S.Pat. No. 5,266,627. The amount of the cross-linking agent can varywidely, depending upon the nature of the ethylenic polymer or thepolymeric composition to be cross-linked, the particular cross-linkingagent employed, the processing conditions, the amount of graftinginitiator, the ultimate application, and other factors. For example,when vinyltrimethoxysilane (VTMOS) is used, the amount of VTMOS isgenerally at least about 0.1 weight percent, at least about 0.5 weightpercent, or at least about 1 weight percent, based on the combinedweight of the cross-linking agent and the ethylenic polymer or thepolymeric composition.

End Use Applications: The ethylenic polymer of this invention may beemployed in a variety of conventional thermoplastic fabricationprocesses to produce useful articles, including objects comprising atleast one film layer, such as a monolayer film, or at least one layer ina multilayer film, which films may be prepared by cast, blown,calendered, or extrusion coating processes; molded articles, such asblow molded, injection molded, or rotomolded articles; extrusions;fibers; woven or non-woven fabrics; and composite or laminate structuresmade with any of the foregoing articles.

The ethylenic polymers of this invention (either alone or in blends orcompounds with other components) may be used in producing fibers, suchas staple fibers, tow, multicomponent, sheath/core, twisted, andmonofilament fibers. Suitable fiber-forming processes include spunbondedand melt blown techniques, as disclosed in U.S. Pat. Nos. 4,340,563(Appel et al.), 4,663,220 (Wisneski et al.), 4,668,566 (Nohr et al.),and 4,322,027 (Reba), gel spun fibers as disclosed in U.S. Pat. No.4,413,110 (Kavesh et al.), woven and nonwoven fabrics, as disclosed inU.S. Pat. No. 3,485,706 (May), or structures made from or with suchfibers, including blends with other fibers (such as polyester, nylon orcotton, and drawn, twisted, or crimped yarns or fibers) or incomposition or laminated structures with fibrous or non-fibrousmaterials (such as nonwovens or films).

The ethylenic polymers of this invention (either alone or in blends orcompounds with other components) may be used in a variety of films,including but not limited to clarity shrink films, collation shrinkfilms, cast stretch films, silage films, stretch hooder films, sealants(including heat sealing films), stand-up-pouch films, liner films, anddiaper backsheets.

The ethylenic polymers are especially useful for making films or filmlayers, preferably wherein the film or film layer is subsequently heatsealed to form a thermally welded bond. The ethylenic polymerspreferably have a peak hot tack in (N/inch) is greater than or equal tothe quantity (13−0.395*12) at a seal bar temperature of from 90 to 140C.

The ethylenic polymers of this invention (either alone or in blends orcompounds with other components) are also useful in other direct end-useapplications, such as for wire and cable coatings, in sheet extrusionfor vacuum forming operations, and forming molded articles, includingarticles made via any of the known thermoplastic molding technologies,including injection molding, blow molding, or rotomolding processes. Thepolymeric compositions of this invention can also be formed intofabricated articles using other conventional polyolefin processingtechniques.

Other suitable applications for the ethylenic polymers of this invention(either alone or in blends or compounds with other components) includefilms and fibers; soft touch goods, such as tooth brush handles andappliance handles; gaskets and profiles; adhesives (including hot meltadhesives and pressure sensitive adhesives); footwear (including shoesoles and shoe liners); auto interior or exterior parts and profiles;foam goods (both open and closed cell); impact modifiers for otherthermoplastic polymers such as high density polyethylene, isotacticpolypropylene, or other olefin polymers; coated fabrics (such asartificial leather); hoses; tubing; weather stripping; cap liners;flooring (such as hard or soft flooring and artificial turf); andviscosity index modifiers, as well as pour point modifiers, forlubricants.

Further treatment of the ethylenic polymers or polymeric compositions ofthis invention may be performed to render them more suitable for otherend uses. For example, dispersions (both aqueous and non-aqueous) canalso be formed using ethylenic polymers or polymeric compositions ofthis invention, such as by a dispersion-manufacturing process. Frothedfoams comprising the embodiment ethylenic polymer can also be formed, asdisclosed in PCT Publication No. 2005/021622. The ethylenic polymers orpolymeric compositions of this invention may also be crosslinked by anyknown means, such as the use of peroxide, electron beam, silane, azide,or other cross-linking technique. The ethylenic polymers or polymericcompositions of this invention can also be chemically modified, such asby grafting (for example by use of maleic anhydride (MAH), silanes, orother grafting agent), halogenation, amination, sulfonation, or otherchemical modification.

All applications, publications, patents, test procedures, and otherdocuments cited, including priority documents, are fully incorporated byreference to the extent such disclosure is not inconsistent with thedisclosed compositions and methods and for all jurisdictions in whichsuch incorporation is permitted.

Examples Resin Production

All raw materials (ethylene, 1-octene) and the process solvent (a narrowboiling range high-purity isoparaffinic solvent trademarked Isopar E andcommercially available from Exxon Mobil Corporation) are purified withmolecular sieves before introduction into the reaction environment.Hydrogen is supplied in pressurized cylinders as a high purity grade andis not further purified. The reactor monomer feed (ethylene) stream ispressurized via mechanical compressor to above reaction pressure at 525psig. The solvent and comonomer (1-octene) feed is pressurized viamechanical positive displacement pump to above reaction pressure at 525psig. The individual catalyst components are manually batch diluted tospecified component concentrations with purified solvent (Isopar E) andpressured to above reaction pressure at 525 psig. All reaction feedflows are measured with mass flow meters and independently controlledwith computer automated valve control systems.

The continuous solution polymerization reactor consists of a liquidfull, non-adiabatic, isothermal, circulating, and independentlycontrolled loop. The reactor has independent control of all freshsolvent, monomer, comonomer, hydrogen, and catalyst component feeds. Thecombined solvent, monomer, comonomer and hydrogen feed to the reactor istemperature controlled to anywhere between 5° C. to 50° C. and typically25° C. by passing the feed stream through a heat exchanger. The freshcomonomer feed to the polymerization reactor is fed in with the solventfeed. The total fresh feed to each polymerization reactor is injectedinto the reactor at two locations with roughly equal reactor volumesbetween each injection location. The fresh feed is controlled typicallywith each injector receiving half of the total fresh feed mass flow. Thecatalyst components are injected into the polymerization reactor throughspecially designed injection stingers and are each separately injectedinto the same relative location in the reactor with no contact timeprior to the reactor. The primary catalyst component feed is computercontrolled to maintain the reactor monomer concentration at a specifiedtarget. The two cocatalyst components are fed based on calculatedspecified molar ratios to the primary catalyst component. Immediatelyfollowing each fresh injection location (either feed or catalyst), thefeed streams are mixed with the circulating polymerization reactorcontents with Kenics static mixing elements. The contents of eachreactor are continuously circulated through heat exchangers responsiblefor removing much of the heat of reaction and with the temperature ofthe coolant side responsible for maintaining isothermal reactionenvironment at the specified temperature. Circulation around eachreactor loop is provided by a screw pump.

The effluent from the first polymerization reactor (containing solvent,monomer, comonomer, hydrogen, catalyst components, and molten polymer)exits the first reactor loop and passes through a control valve(responsible for maintaining the pressure of the first reactor at aspecified target). As the stream exits the reactor it is contacted withwater to stop the reaction. In addition, various additives such asanti-oxidants, can be added at this point. The stream then goes throughanother set of Kenics static mixing elements to evenly disperse thecatalyst kill and additives.

Following additive addition, the effluent (containing solvent, monomer,comonomer, hydrogen, catalyst components, and molten polymer) passesthrough a heat exchanger to raise the stream temperature in preparationfor separation of the polymer from the other lower boiling reactioncomponents. The stream then enters a two stage separation anddevolatization system where the polymer is removed from the solvent,hydrogen, and unreacted monomer and comonomer. The recycled stream ispurified before entering the reactor again. The separated anddevolatized polymer melt is pumped through a die specially designed forunderwater pelletization, cut into uniform solid pellets, dried, andtransferred into a hopper. After validation of initial polymerproperties the solid polymer pellets are manually dumped into a box forstorage. Each box typically holds ˜1200 pounds of polymer pellets.

The non-polymer portions removed in the devolatilization step passthrough various pieces of equipment which separate most of the ethylenewhich is removed from the system to a vent destruction unit (it isrecycled in manufacturing units). Most of the solvent is recycled backto the reactor after passing through purification beds. This solvent canstill have unreacted co-monomer in it that is fortified with freshco-monomer prior to re-entry to the reactor. This fortification of theco-monomer is an essential part of the product density control method.This recycle solvent can still have some hydrogen which is thenfortified with fresh hydrogen to achieve the polymer molecular weighttarget. A very small amount of solvent leaves the system as a co-productdue to solvent carrier in the catalyst streams and a small amount ofsolvent that is part of commercial grade co-monomers.

Unless otherwise stated, implicit from the context or conventional inthe art, all parts and percentages are based on weight.

Comparative Sample E and Examples 6 and 7: Ethylenic polymers areprepared in order to compare the properties of ethylene-octene polymers(Comparative Example E) prepared using a known metallocene catalyst tothe properties of ethylene-octene polymers (Examples 6 and 7) of thisinvention. Each ethylenic polymer is prepared in plant operatingsubstantially in accordance with the resin production section above.

Table 1 describes the polymerization conditions used to produce each ofthe copolymers.Table 2 lists various properties of those polymers.

TABLE 1 Reactor C₂ Corrected Reactor H₂ Octene/ MI Temp Solvent/ ConvExit C2 Poly Conc. Mole Olefin Run Example Catalyst (I₂) Density (C.) C2Ratio (%) (g/L) (Wt %). % Ratio Lot Comp E 1301/RIBS2/MMAO 0.98 0.901XB1401E132 2009C03R09 6 6114/RIBS2/MMAO 1.13 0.900 120.9 4.49 86.5 15.219.31 1.075 40.98 2009C03R09 7 6114/RIBS2/MMAO 0.98 0.897 138.7 4.5185.9 16.2 19.2 0.459 40.98 140 C. CAS name for RIBS-2: Amines,bis(hydrogenated tallow alkyl)methyl,tetrakis(pentafluorophenyl)borate(1-) CAS name for DOC-6114: Zirconium,[2,2″′-[1,3-propanediylbis(oxy-κO)]bis[3″,5,5″-tris(1,1-dimethylethyl)-5′-methyl[1,1′:3′,1″-terphenyl]-2′-olato-κO]]dimethyl-,(OC-6-33)- MMAO = modified methyl aluminoxane CAS name for CGC 1301:

TABLE 2 Melt Flow Zero Shear DSC Ratio Viscosity ZSV Melting g′ (HMW)/Example Catalyst I10/I2 Mw Mn Mw/Mn Pa-s 190 C. Ratio point (C.) g′(LMW) Comp E 1301/RIBS2/MMAO 9.1 89760 36740 2.44 13029 4.75 98.5 0.9506 6114/RIBS2/MMAO 6.3 99620 44540 2.24 7610 1.89 96.4 7 1301/RIBS2/MMAO6.4 103100 47080 2.19 8776 1.93 98.9 0.967The film-fabrication conditions are described in Table 3.

TABLE 3 Sample ID EXAMPLE 6 Inventive Comparative E Comparative RunNumber 09C03R09 XB1401E132 Coex Coex B—ATTANE B—ATTANE A—Example 64201/AMPLIFY C—Ultramid A—Comparative 4201/AMPLIFY C—Ultramid w/DOC 6114GR-205, 90/10 C33L01 Ex. E GR-205, 90/10 C33LO1 Melt Temperature C. 184225 185 226 Screw Speed rpm 66 72 49 66 72 49 Motor Amps A 4.8 6.5 2.24.1 6.3 2.2 Melt Back Pressure bar 283 346 101 247 339 99 Feed Rate kg/h2.8 6.8 3.1 3 6 3 Sample ID Example 7 Inventive Run Number 09C03R09 140°C. Coex B—ATTANE A—Example 7 4201/AMPLIFY C—Ultramid w/DOC-6114 GR-205,90/10 C33L01 Melt Temperature C. 185 225 Screw Speed rpm 66 72 49 MotorAmps A 4.9 6.9 2.3 Melt Back Pressure bar 306 374 103 Feed Rate kg/h 2.76 3.1 Film Structure Outer Layer C Core B Sealant A

TABLE 4 Hot Tack data that is in graph above. Example 60 C. 70 C. 80 C.90 C. 100 C. 110 C. 120 C. 130 C. 140 C. 150 C. Comp. E 0.242 0.356 2.345.49 10.12 8.71 8.97 7.78 8.79 12.42 6 0.264 0.604 1.59 4.67 15.86 16.7111.90 12.70 11.75 5.81 7 0.258 0.276 1.08 3.51 13.03 15.52 12.92 12.1211.70 9.00

Comparative Sample E and Examples 6 and 7: Three ethylenic polymers areprepared in order to compare the hot tack strength and sealing windowproperties of a ethylene-octene polymer (Comparative Samples E) preparedusing a known constrained geometry metallocene catalyst to theproperties of two ethylene-octene polymers (Examples 6 and 7) of thisinvention when fabricated into a sealant layer in a multilayer film.Each ethylenic polymer is prepared in the same pilot plant as describedabove for Examples 1 through 5.

The polymers of Comparative Sample E and of Examples 6 and 7 are thenfabricated into sealant-layer A of a three-layer film of the structureA/B/C. Layers B and C are the same for each case, with layer Bcomprising a 90/10 blend of ATTANE™ ULDPE polymer with AMPLIFY™ GR 205functionalized polymer (both available from The Dow Chemical Company),and layer C comprising ULTRAMID® C 33L 01 polyamide made by BASFCorporation is a Nylon 66/6 (Polyamide 66/6 Copolymer) plastic material.

1. An ethylenic polymer having: an overall polymer density of not morethan 0.905 g/cm³; a GI200 gel rating of not more than 15; 110/12(measured at 190° C.) from about 5.8 to about 6.5, preferably from about5.9 to about 6.5; a zero shear viscosity (ZSV) ratio of from about 1.3to about 2.3, preferably from about 1.4 to about 2.2, most preferablyfrom about 1.5 to about 2.1; and Mw/Mn of from about 2.0 to about 2.4,preferably from about 2.1 to about 2.3; and a g′(HMW)/g′(LMW) of greaterthan 0.95.
 2. The ethylenic polymer of claim 1 further comprising a havemelt index (190° C., 2.16 kg load) from about 0.5 to about 15 gms/10minutes, preferably from about 0.7 to about
 12. 3. The ethylenic polymerof claim 1 further comprising a DSC melting point defined by therelationship,Tm(° C.)≦(−7914.1*(density)2)+(15301*density)−7262.4, where density isin g/cc.
 4. The ethylenic polymer of claim 1 wherein the density is fromabout 0.857 g/cc to 0.905 g/cc, preferably from about 0.865 g/cc to0.905 g/cc, most preferably from about 0.885 g/cc to 0.905 g/cc.
 5. Acomposition comprising, or made from, at least one ethylenic polymer ofclaim 1, wherein at least a portion of the ethylenic polymer has beencross-linked.
 6. A composition comprising, or made from, at least oneethylenic polymer of claim 1, in which at least a portion of theethylenic polymer has been functionalized.
 7. A composition comprising,or made from, at least one ethylenic polymer of claim 1 and at least oneother natural or synthetic polymer.
 8. The composition of claim 11 inwhich at least one of the other natural or synthetic polymer(s) isselected from the group consisting of at least one thermoplastic orelastomeric olefin polymer and at least one styrenic block copolymer. 9.A composition comprising, or made from, at least one ethylenic polymerof claim 1 and at least one other component selected from the groupconsisting of a tackifier, a wax, and an oil.
 10. A compositioncomprising a dispersion or emulsion of particles in a fluid, wherein theparticles comprise, or are made from, at least one ethylenic polymer ofclaim
 1. 11. A fabricated article in which at least one layer or portionof the fabricated article comprises, or is made from, at least oneethylenic polymer of claim
 1. 12. The fabricated article of claim 10 inwhich the fabricated article comprises a film, a sheet, a fiber, anonwoven, a laminate, or a composite.
 13. The fabricated article ofclaim 11 in which the article is a multilayer film and the layer of thefilm that comprises, or is made from, the at least one ethylenic polymerhas a peak hot tack in (N/inch) is greater than or equal to the quantity(13−0.395*12) at a seal bar temperature of from 90 to 140 C.